• Title/Summary/Keyword: Pretransition Oxide

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Microscopic characterization of pretransition oxide formed on Zr-Nb-Sn alloy under various Zn and dissolved hydrogen concentrations

  • Kim, Sungyu;Kim, Taeho;Kim, Ji Hyun;Bahn, Chi Bum
    • Nuclear Engineering and Technology
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    • v.50 no.3
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    • pp.416-424
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    • 2018
  • Microstructure of oxide formed on Zr-Nb-Sn tube sample was intensively examined by scanning transmission electron microscopy after exposure to simulated primary water chemistry conditions of various concentrations of Zn (0 or 30 ppb) and dissolved hydrogen ($H_2$) (30 or 50 cc/kg) for various durations without applying desirable heat flux. Microstructural analysis indicated that there was no noticeable change in the microstructure of the oxide corresponding to water chemistry changes within the test duration of 100 days (pretransition stage) and no significant difference in the overall thickness of the oxide layer. Equiaxed grains with nano-size pores along the grain boundaries and microcracks were dominant near the water/oxide interface, regardless of water chemistry conditions. As the metal/oxide interface was approached, the number of pores tended to decrease. However, there was no significant effect of $H_2$ concentration between 30 cc/kg and 50 cc/kg on the corrosion of the oxide after free immersion in water at $360^{\circ}C$. The adsorption of Zn on the cladding surface was observed by X-ray photoelectron spectroscopy and detected as ZnO on the outer oxide surface. From the perspective of $OH^-$ ion diffusion and porosity formation, the absence of noticeable effects was discussed further.

Experimental Verification of a Kinetic Model of Zr-Oxidation

  • Yoo, Han-Ill;Park, Sang-Hyun
    • Journal of the Korean Ceramic Society
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    • v.43 no.11 s.294
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    • pp.724-727
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    • 2006
  • It has long been known that the oxidation kinetics of Zr-based alloys undergoes a crossover from parabolic to cubic in the pretransition period (before breakaway of the oxide scale). This kinetic crossover, however, is not fully understood yet. We have earlier proposed a model for the Zr-oxidation kinetics, in a closed form for the first time, by taking into account a compressive strain energy gradient as a diffusional driving force in addition to a chemical potential gradient of component oxygen across the ZrO$_2$ scale upon Zr [J. Nucl. Mater., 299 (2001) 235]. In this paper, we experimentally reconfirm the validity of the proposed model by using the thermogravimetric data on mass gain of Zr in a plate and wire form, respectively, in air atmosphere at different temperatures in the range of 500$^{\circ}$ to 800$^{\circ}C$, and subsequently report on the numerical values for oxygen chemical diffusivity and strain energy gradient across the oxide scale.

Corrosion Characteristics and Oxide Microstructure of Zirconium Alloys for Nuclear Fuel Cladding (핵연료피복관용 Zr 합금의 부식특성 및 산화막 미세구조)

  • Jeong, Yong-Hwan;Baek, Jong-Hyeok;Kim, Seon-Jae;Kim, Gyeong-Ho;Choi, Byeong-Gwon;Jung, Yeon-Ho
    • Korean Journal of Materials Research
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    • v.8 no.4
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    • pp.368-374
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    • 1998
  • The corrosion characteristics of zirconium alloys have been investigated in various aqueous solutions of LiOH. NaOH, KOH, RbOH. and CsOH at 3S$0^{\circ}C$. The concentrations of solutions were set to 4.3 mmol and 32.Smmol with equimolar $M^+$ and OH . The oxide characterization was performed using TEM on the samples corroded in 32. Smmol LiOH, NaOH, and KOH solution. The samples were prepared to have the same oxide thickness for the pretransition and post- transition regimes. Considering the trend of experimental data, the cation would playa major role in the corrosion process of Zr alloys in alkali hydroxide solutions. The microstructures of the oxides formed in various solutions were quite different. In LiOH solution the oxides grown in pre-transition as well as post-transition had the equiaxed structures with many pores and open grain boundaries. The oxides grown in NaOH solution had the protective columnar structures in pre-transition and the equiaxed structures with many open grain boundaries in post- transition. On the other hand. in KOH solution the columnar structure was maintained from pre- transition to post- transition. It was considered that the cation incorporation into zirconium oxide controlled the oxide characteristics and the corrosion acceleration in alkali hydroxide solutions.

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